Paint



Patented July 2, 1946 2,403,423 PAINT Paul Zurcher, Ponca City, Okla., assignor to Continental Oil Company, Ponca City, Okla., a corporation of Delaware No Drawing. Application June 26, 1943, Serial No. 492,447

My invention relates broadly to. paints andmore particularly'to a paint containing a halogenated organic compound and an amine.

This application is a continuation-in-part of my co-pending application Serial No. 368,227, filed December 2, 1940, which in turn, is a continuation-in-part of my co-pending applications Serial No. 296,445, filed September 25, 1939, and

immediately converted to ammonium bases in the presence of water and in the converted state are no longer eflicacious to improve the paint.

The vehicle may be any drying vegetable oil, such as linseed oil, tung oil, oiticica oil, or perilla oil; it may consist of a solution of natural or synthetic resins, including chlorinated rubber in suitable solvents; it may be a combination of the above two classes; or it may be a solution of v cellulose acetate or cellulose nitrate. All of the above vehicles possess the common characteristic that they form a hard, dry, elastic film after being spread on a surface. This is true although the cause of drying may be different. The vehicles may dry with or without catalysts, by oxidation, polymerization, or both, or by simple evaporation of a. volatile solvent. I

Pigments are defined as the fine solid particles used in the preparation of paints and substantially insoluble in the vehicle. I do not consider asphaltic materials from any source as pigments.

In my first application Serial No. 175,775, filed November 22, 1937, I disclose broadly that halogenated organic compounds when added to a paint in small amounts will improve the physical and chemical qualities of the paint film.

In my copending application Serial No. 295,445,

filed September 25, 1939, I disclose the beneficial and improved results obtained from the addition to a paint of an amine.

I have now discovered that if small amounts of both a halogenated organic compoundand an amine are dissolved in the paint vehicle, unexpected and improved results are obtained that are not achieved by either of these compounds alone. The individual advantages obtained by each compound are, of course, still obtained.

I am aware of the fact that others have incorporated protective and volatile toxic chemicals into paints by combining the chemicals under enormous pressurewith the paint pigments. However, in this case, the additives have no in- 4 Claims. (Cl. 106-263) fluence on the physical or chemical properties of the liquid paints nor do they change the film after it has dried. When thus incorporated into the paint the chemicals act entirely difl'erently than when dissolved by the vehicle and are intended only to protect the covered surface after the paint mm has ruptured. Until this occurs they are merely held as inert constituents of the paint.

When the amines alone are added to a paint they frequently so increase the viscosity, of the paint that it can no longer be easily applied or brushed onto a surface, On the other hand, the addition of a halogenated organic compound frequently so reduces the viscosity of the paint that it no longer has the requisite hiding power. Furthermore, many halogenated organic compounds have the undesirable property of accelerating the formation of a tough surface skin during storage of the paint.

I have found that the harmful effects of both classes of additives can be eliminated if the thin-.

ning tendency of the halogenated organic compounds is counteracted by the thickening tendency of the mines. Also, when these two classes of compounds are added together the amines have the unexpected property of inhibiting skin formation caused during storage by the halogenated organic compound. Moreover, by adding both classes of compounds together, I can produce a paint having greater durability, luster, depth of color, and elasticity. At the same time, I do not impair but improve the hiding power of the paint. Furthermore, I find that both of the compounds eliminate completely such serious defects of the paint film as checking or peeling, although neither alone will eliminate or improve these defects.

By halogenated organic compounds, I mean organic compounds having a vapor pressure of less than atmospheric at 170 F., containing halogen, carbon, generally hydrogen and perniissively oxygen and. other elements. The preferred compounds are halogenated aliphatic esters and halogenated waxes. However, the esters may be ali-= phatic, aromatic or heterocyclic. The less complex, i. e., the aliphatic and lower molecular weight esters, are generally preferred, although the more complex esters, i. e., the higher molecular weight and the aromatic -and. heterocyclic esters, are effective when the paint is very thin. As a general rule, halogenated compounds containing one or more benzene rings increase the viscosity of the paint.

The second component of this invention, the amine, may be'any organic compound having the amine radical. The amine may be primary, secondary, or tertiary. The NH: radical may be present, as'such, or one or both of the hydrogens may be replaced by organic radicals which may be aliphatic, aromatic, or heterocyclic. The

amines may contain other elements in addition to carbon, hydrogen and nitrogen. In fact, the presence of oxygen seems to improve the beneficial activity of the amine in many cases. In general I prefer not to use amines of low flash point because of their toxicity. The following examples are, of course, not inclusive; they are, however, representative of suitable amines within the above general definition:

1. Dibutyl amine 2. Tributyl amine Diamyl amine 'I'riamyl amine Diethyl-amino ethanol Di-n-butyl arnino ethanol Dipropyl-ethanol amine Aniline Ortho-toluidine Meta-toluidine Para-toluidine Xylidines Monomethyl aniline Para-phenylene diamine 15. Pyridine the paints. For example, an excess of the compounds causes increased drying time, objectionable odor, dull spots, and a film of reduced dura-' bility. These undesirable properties are easily detected. While it is to be understood that certain compounds can be added in larger amounts than other similar 01 related compounds without adversely aifecting the paint; as a general rule, between 0.1 per cent and 2.5 per cent of each of the two additives is the range within which favorable results are obtained.

Of course, diiferent members of the two classes of compounds may improve or affect different properties in a paint. The same member may act differently in different paints. However, the

desired result can be achieved by a judicious selection of the additives based on an examination and knowledge of the base paint. The following examples demonstrate the joint effect or an amine and a halogenated organic compound on different properties of paints.

-E.rample 1.-The effect on the viscosity of a paint by the addition of an amine and a halogenated organic compoundis shown in this example. All viscosity determinations were made with a Ford viscosity cup having a No. 4 orifice and at a temperature of 75 Fahrenheit. A heavy black primer paint consisting of black iron oxlde, carbon black, and red lead as pigments, and linseed oil, thinner and drier as vehicle was selected. The viscosity of this paint was 136. The

same paint plus one per cent methyl dichlorostearate alone had a viscosity of 104, while the same paint plus 0.4 per cent triamyl amine alone had a viscosity of 92. When one per cent methyl dichlorostearate and 0.4 per cent triamyl amine were both added to the paint its viscosity was reduced to 85.

The above illustrates the manner in which the viscosity of an extremely heavy paint can be changed at will by the judicious selection of additives embodying the invention without dilution by oil or the use of a thinner. Thus, by using the additives the paint can be made to flow easily without appreciably affecting its composition.

Example 2.-The following test further illustrates the manner in which the viscosity of a paint can be controlled by judiciously selecting the additives for a particular paint. An exterior paint containing 63 per cent pigment (titanium dioxide and zinc oxide) and 37 per cent 'vehicle (linseed oil and drier) was used in this test. When this paint was diluted with linseed oil in the proportion of 4:1, it had a viscosity of 49.

The addition of one and one-half per cent methyl 'dichlorostearate further reduced the viscosity of the paint to 45, making it .too thin for brushing, while the addition of one-half of one per cent of diethanol amine increased the viscosity of the paint to 55 rendering it too sticky. The combined action of the two compounds brought the viscosity of the paint back to 49, and at the same time, materially improved the fiow and brushability of" the original paint.

The addition of chlorinated wax and diethanol amine in the same proportions as the above. raised the viscosity of the paint to 51, and improved its hiding power.

One-half per cent of diethanol amine and one and onehalf per cent of chlorophenyl mercaptan, dichlorophenyl oxide, pentachloro benzene, and pentachloro-phenyl benzoate changed the viscosity of the paint to 68, 62, 55 and 70, respectively.

Other eifects of the combination of a halogenated compound and an amine are shown in the following examples:

Example 3.-This test shows the effect of the additives upon skin formation. A synthetic green enamel was selected which consisted of 14.5 per cent pigment (chrome green) and 85.5 per cent vehicle (glycerol phthalic resin solution). After storage for one week this paint had formed a skin on its surface. Another sample of the same paint, containing one per cent by weight of methyl dichlorostearate, also formed a skin after one week's storage. A third sample of the same synthetic enamel, containing one per cent by weight of chlorinated China-wood oil, formed a very heavy skin in the same time. To determine the effect of an amine on the above points, each of the three samples was divided into four portions. One per cent tri-ethanol amine was added to one portion ofeach sample, one per cent diethanol amine was added to the second portions of the samples. one per cent diamyl amine was added to the third portions of the same and one per cent triamyl amine was added to the fourth portions thereof. Each portion of. the first sample, 1. e., the paint containing an amine but no halogenated organic compound,- continued to form a surface skin as before; however, the samples containing the amines in addition to the halogenated compounds developed no skinning whatever after one month's storage. This result is unexpected. Samples containing a halogenated organic compound, alone, and samples containing an amine, alone, soon formed a surface skin during storage. However,

the samples containing both of these additives formed no surface skin even after storage for a considerable length of time.

Example 4.--Thls test further illustrates the effect of the two additives on the skin forming tendency of paints. A white oil-base enamel in which the vehicle comprises a mixture of Chinawood oil, linseed oil, resins and drier, and the pigment was a mixture of titanium dioxide and zinc oxide, developed a surface skin within two weeks of storage. The same enamel with one per cent methyl dichlorostearate formed a. heavier skin. The same enamel with one per cent chlorinated China-wood oil formed a skin within a few hours; and, after two weeks, the skin was a hard, hornlike texture. Samples of the enamel containing one per cent chlorinated China-wood oil and of the enamel containing one per cent methyl dichlorostearate were prepared with a further addition of one per cent by weight of diethyl-amino ethanol. After two weeks of storage, no skin had lformed in the containers.

rinated China-wood oil was added. This sample To one of the above two samples an additional 1 /2 per cent of chlo-' showed a rapid tendency to form a skin; howwas coated with a sample of the enamel to which no additives had been added. A second panel was coated with a sample of the enamel to which had been added one per cent of methyl dichlorostearate. A third panel was coated with a sample of the enamel to which had been added 0.5 per cent tributyl amine, and a fourth panel was coated with a sample of the enamel containing one per cent methyl dichlorostearate and 0.5 per cent tributyl amine. All four of these panels were placed in an accelerated weathering machine and subjected to conditions corresponding to two years exposure to the atmosphere. At the end of the testing period, the following resuits were observed.

The filni containing no addition, the film containing one per cent of methyl dichlorostearate and the film containing 0.5 per cent of tributyl amine, all had the undesirable golden-purple hue known to the trade as bronzing, while the film containing one per cent methyl dichlorostearateplus 0.5 per cent tributyl amine was perfectlyiblack.

After the chalk had been wiped from the film surfaces, the films showed drastic dilierences. The filmcontaining no additive was badly cracked on. its whole surface. The film containing one per cent of methyl dichlorostearate was so severely checked "that it was partly disintegrated. In the latter film the pattern ofthe checks had been changed from. an irregular network to parallel straight lines. The addition of 0.5 per cent tributyl amine had no apparent effect on the checking since the amine containing film looked very similar to the one containing no additives. 0n the other hand, the film containing one per cent methyl dichlorostearate and 0.5 per cent tributyl amine was by far the best preserved although exposed to weathering fifty per cent longer than the other three films. A few very fine, disconnected hair checks could be detected only with a magnitying glass.

Example 6.The eflect on the physical properties of the paint film by the addition of my additives is further brought out by the following example. A paint was selected comprising a red iron oxide suspended in a vehicle consisting of linseed oil, a thinner, and a drier. This paint was defective in that it had a, tendency to detach itself from the coated surface. Four panels were prepared, one being coated with a sample of the paint containing no additives, the second being coated with a sample of the paint containing 0.5 per cent methyl dichlorostearate, the third being coated with a sample of the paint containing 0.4 per cent of aniline and the fourth being coated with a sample of the paint containing 0.5 per cent of methyl dichlorostearate and 0.4 per cent of aniline. Two coats of each paint sample was sprayed on its respective panel. For comparative purposes, four additional panels were prepared, each panel having one coat of a respective one of the above paint samples brushed thereon. The first set of'panels having two coats of paint were subjected to accelerated weathering for 490 hours. The second set of single-coated panels wereexposed to atmospheric weathering for- 123 days. Both sets of panels gave identical results, the ones- .exposed to atmospheric weathering being more pronounced because of the single coat In both sets of panels the film's without additions were full'of pinholes. Moreover, much of the paint had fallen from the surface of the single coated panel. The filmscontaining 0.5 per cent methyl 'dichlorostearate only, and the films containing aniline only were even more deteriorated than the above films. It is significant, therefore, that both panels coated with paint containing 0.5 percent methyl dichlorostearate and 0.4 per cent aniline showed no evidence of pinholes or loosening of the paint mm.

It is believed that the above examples clearly establish that newand unexpected results are pigment dispersion is'increased; and, when spread out, the tinting strength of the pigment is'improved and the dry films have better adhesion. to the surface, as well as greater durability and higher surface gloss.

Having thus described my invention, I claimz' 1. A non-aqueous paint comprising a drying oil vehicle having the characteristics of forming a hard, dry elastic film after being applied to a sur face, said vehicle having added'thereto methyl dichlorostearate in amounts ranging from about .001 per cent to about 2.5 per cent of the paint composition, said paint also including a, high flash point amine from the group consisting of triethanol amine, diethanol amine, triamyl amine, tributyl amine and aniline to reduce the skin forming tendency oi the paint, said amine being present in amounts ranging from about 0.l per cent to about 2.5 per cent of the paint composition. a

2. A paint as set forth in cl 1 in which the amine is tri-amyl amine.

3. A paint as set forth in claim 1 in which the amine is tri-ethanol amine.

4. A r as set forth in claim 1 in which the amine is aniline.

PAUL ZCR. 

